The present invention relates to novel phthalocyanines of the formula I 
where
Me is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AlCl, AlOH, AlOCOCH3, AlOCOCF3, SiCl2 or Si(OH)2,
at least four of the radicals R1 to R16 are each independently of the others a five- or six-membered saturated nitrogen-containing heterocyclic radical which is bonded to the phthalocyanine structure via a ring nitrogen atom and which can additionally contain one or two further nitrogen atoms or a further oxygen or sulfur atom, and
any remaining radicals R1 to R16 are each hydrogen, halogen, hydroxysulfonyl or C1-C4-dialkylsulfamoyl,
subject to the proviso that tetrakispiperidinylphthalocyanine shall be excluded,
to the use of heterocyclyl-substituted phthalocyanines for marking liquids, and to mineral oils comprising such phthalocyanines.
J. Gen. Chem. USSR, 51 (1981), 1405-1411, discloses the preparation of tetrakispiperidinylphthalocyanine. WO-A-94/02570 and WO-A-96/10620 describe phthalocyanines as markers for liquids, especially mineral oils.
However, it has been found that the markers described therein still have defects in their application properties, especially insufficient solubility and insufficient chemical stability in solution.
It is an object of the present invention to provide suitable phthalocyanines having an improved property profile.
We have found that this object is achieved by the phthalocyanines of the formula I more particularly defined at the beginning.
Any alkyl appearing in the formulae mentioned herein may be straight-chain or branched.
Halogen is for example fluorine, chlorine, bromine or iodine.
C1-C4-Dialkylsulfamoyl is for example dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, diisopropylsulfamoyl, dibutylsulfamoyl or N-methyl-N-ethylsulfamoyl.
Suitable five- or six-membered saturated nitrogen-containing heterocyclic radicals which are attached to the phthalocyanine structure via a ring nitrogen atom and can additionally contain one or two further nitrogen atoms or a further oxygen or sulfur atom in the ring are derived for example from pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isoxazolidine, piperidine, piperazine, morpholine or thiomorpholine as basic structure.
The heterocyclic radicals can be monosubstituted or polysubstituted, preferably monosubstituted, disubstituted or trisubstituted, especially monosubstituted. Preferred substituents are C1-C4-alkyl, benzyl, phenylethyl or phenyl.
Suitable heterocyclic radicals are for example pyrrolidin-1-yl, 2- or 3-methylpyrrolidin-1-yl, 2,4-dimethyl-3-ethylpyrrolidinyl, pyrazolidin-1-yl, 2-, 3-, 4- or 5-methylpyrazolidin-1-yl, imidazolidin-1-yl, 2-, 3-, 4- or 5-methylimidazolidin-1-yl, oxazolidin-3-yl, 2-, 4- or 5-methyloxazolidin-3-yl, isoxazolidin-2-yl, 3-, 4- or 5-methylisoxazolidin-2-yl, piperidin-1-yl, 2-, 3-, 4-methyl-, -ethyl- or -benzyl-piperidin-1-yl, 2,6-dimethylpiperidin-1-yl, piperazin-1-yl, 4-(C1-C4-alkyl)piperazin-1-yl, such as 4-methyl- or 4-ethylpiperazin-1-yl, morpholin-4-yl, thiomorpholin-4-yl or thiomorpholin-4-yl S,S-dioxide.
Preferred heterocyclic radicals are derived from pyrrolidine, piperidine, piperazine or morpholine as basic structure.
Preference is given to phthalocyanines of the formula I wherein four of the radicals R1 to R16 are each a heterocyclic radical.
Preference is further given to phthalocyanines of the formula I wherein four of the radicals R1 to R16 are each a heterocyclic radical and the remaining radicals R1 to R16 are each hydrogen.
Preference is further given to phthalocyanines of the formula I which have heterocyclic radicals which are monosubstituted or polysubstituted, preferably monosubstituted, disubstituted or trisubstituted, especially monosubstituted, by C1-C4-alkyl, benzyl, phenylethyl or phenyl.
Preference is given to phthalocyanines which conform to the formula Ia or Ib 
where
the radicals R4, R8, R12 and R16 and also R2, R6, R10 and R14 are each a heterocyclic radical and Me is in each case as defined above, and also their positional isomers in relation to the radicals R4, R8, R12 and R16 and also R2, R6, R10 and R14.
Of particular interest are phthalocyanines of the formula Ia or Ib, where R4, R8, R12 and R16 and also R2, R6, R10 and R14 are each pyrrolidin-1-yl, piperidin-1-yl, piperazin-1-yl or morpholin-4-yl, which radicals can be monosubstituted, disubstituted or trisubstituted, preferably monosubstituted, by C1-C4-alkyl, benzyl, phenylethyl or phenyl.
Preference is also given to phthalocyanines of the formula I in which the substituents are selected from a combination of the above-recited preferred substituents.
The novel phthalocyanines of the formula I are obtainable in a conventional manner, for example as described in J. Gen. Chem. USSR 51 (1981) 1405-1411, F. H. Moser, A. L. Thomas, The Phthalocyanines, CRC Press, Boca Rota, Fla., 1983, or J. Am. Chem. Soc. 106 (1984) 7404-7410. For instance, phthalonitriles which, in conformance with the formula I, bear suitable substituents can be made to react in an inert diluent in the presence of a base, optionally in the presence of a metallizing reagent.
The present invention further provides for the use of phthalocyanines of the formula II 
where
Me is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AlCl, AlOH, AlOCOCH3, AlOCOCF3, SiCl2 or Si(OH)2,
at least four of the radicals R1 to R16 are each independently of the others a five- or six-membered saturated nitrogen-containing heterocyclic radical which is bonded to the phthalocyanine structure via a ring nitrogen atom and which can additionally contain one or two further nitrogen atoms or a further oxygen or sulfur atom, and
any remaining radicals R1 to R16 are each hydrogen, halogen, hydroxysulfonyl or C1-C4-dialkylsulfamoyl,
as markers for liquids.
Preference is given to the use of phthalocyanines of the formula I wherein four of the radicals R1 to R16 are each a heterocyclic radical.
Preference is further given to the use of phthalocyanines of the formula I wherein four of the radicals R1 to R16 are each a heterocyclic radical and the remaining radicals R1 to R16 are each hydrogen.
Preference is further given to the use of phthalocyanines of the formula I which have heterocyclic radicals which are monosubstituted or polysubstituted, preferably monosubstituted, disubstituted or trisubstituted, especially monosubstituted, by C1-C4-alkyl, benzyl, phenylethyl or phenyl.
Particular preference is given to the use of phthalocyanines which conform to the formula Ia or Ib 
where
the radicals R4, R8, R12 and R16 and also R2, R61 R10 and R14 are each a heterocyclic radical and Me is in each case as defined above, and also their positional isomers in relation to the radicals R4, R8, R12 and R16 and also R2, R6, R10 and R14.
Of particular interest is the use of phthalocyanines of the formula Ia or Ib, where R4, R8, R12 and R16 and also R2, R6, R10 and R14 are each pyrrolidin-1-yl, piperidin-1-yl, piperazin-1-yl or morpholin-4-yl, which radicals can be monosubstituted, disubstituted or trisubstituted, preferably monosubstituted, by C1-C4-alkyl, benzyl, phenylethyl or phenyl.
It is frequently necessary to mark liquids in order that the liquids thus marked may be detected later, for example in use, by means of suitable methods.
In this way it is possible, for example, to distinguish fuel oil and diesel oil.
Suitable solvents for marking according to the invention by means of the compounds more particularly defined above are especially organic liquids, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, isopentanol, neopentanol or hexanol, glycols, such as 1,2-ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 2,3- or 1,4-butylene glycol, di- or triethylene glycol or di- or tripropylene glycol, ethers, such as methyl tert-butyl ether, 1,2-ethylene glycol monomethyl or dimethyl ether, 1,2-ethylene glycol monoethyl or diethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran or dioxane, ketones, such as acetone, methyl ethyl ketone or diacetone alcohol, esters, such as methyl acetate, ethyl acetate, propyl acetate or butyl acetate, aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, mineral spirit, mineral oils, such as gasoline, kerosene, diesel oil or fuel oil, natural oils, such as olive oil, soybean oil or sunflower oil, or natural or synthetic engine, hydraulic or gear oils, for example vehicle engine oil or sewing machine oil, or brake fluids.
The abovementioned compounds are particularly useful for marking mineral oils where some form of identification is mandatory, for example for tax reasons. To keep the costs for this to a minimum, it is usually desirable to use very high yield dyes for the coloring. However, even so-called strong dyes are no longer detectable purely visually in high dilution in mineral oils.
Based on the weight of the liquid to be marked, from 1 to 1000 ppb, preferably from 1 to 500 ppb, especially from 100 ppb to 500 ppb, of phthalocyanine II are used.
To mark the liquids, especially mineral oils, the phthalocyanines of the formula II are generally employed in the form of solutions. Suitable solvents are preferably aromatic hydrocarbons, such as C1-C20-alkyl-substituted aromatic hydrocarbons, for example toluene, xylene or Shellsol(copyright) (from Shell). To avoid the resulting solutions having an excessively high viscosity, the concentration of phthalocyanine II is generally chosen within the range from 0.5 to 60% by weight, based on the solution.
The present invention further provides mineral oils comprising one or more phthalocyanines of the formula II.
The phthalocyanines II generally have their absorption maximum within the range from 600 to 1200 nm and/or fluoresce within the range from 620 to 1200 nm and are thus easy to detect using suitable instruments.
The detection of the phthalocyanines II can be effected in a conventional manner, for example by measuring the IR absorption spectrum of the liquids to be examined.
However, it is also possible to excite the fluorescence of the phthalocyanines II present in the liquids, advantageously using a semiconductor laser or a semiconductor diode. It is particularly advantageous to employ a semiconductor laser or diode having a maximum emission wavelength within the spectral region from xcexmax xe2x88x92100 nm to xcexmax +20 nm. Here xcexmax is the wavelength of the absorption maximum of the marker. The maximum emission wavelength is within the range from 620 to 1200 nm.
The fluorescence light thus generated is advantageously detected using a semiconductor detector, especially with a silicon photodiode or a germanium photodiode.
Detection is accomplished particularly advantageously when the detector is disposed behind an interference filter and/or a cutoff filter (having a short wave transmission cutoff within the range from xcexmax to xcexmax +80 nm) and/or a polarizer.
By means of the abovementioned compounds, it is very simple to detect marked liquids, even if the phthalocyanines II are present only in a concentration of about 1 ppm (detection by absorption) or about 5 ppb (detection by fluorescence).
The phthalocyanines of the formula II are highly soluble in the liquids to be marked. They also have high chemical stability in solution.